Phosphorus-containing amidines

ABSTRACT

COMPOUNDS OF THE FORMULA:   R-P(=X)(-R1)-N=C(-R2)-NH2   IN WHICH R IS LOWER ALKYL OR LOWER ALKOXY: R1 IS LOWER ALKOXY OR LOWER ALKYLTHIO R3 IS HYDROGEN, LOWER ALKYL PHENYL: MONO OR DI-SUBSTITUTED PHENYL: AND X IS OXYGEN WHEN R1 IS LOWER ALKYLTHIO AND SULFUR WEN R1 IS LOWER ALKOXY AS INSECTICIDES AND ACARICIDES, AND A PROCESS FOR PREPARING THE COMPOUNDS ABOVE HAVING X BE OXYGEN.

United States Patent 3,825,632 PHOSPHORUS-CONTAINING AMIDINES Ferenc M. Pallos, Pleasant Hill, Calif., assignor to Stauifer Chemical Company, New York, NY.

No Drawing. Original application Dec. 15, 1969, Ser. No. 885,263, now Patent No. 3,734,980. Divided and this application July 24, 1972, Ser. No. 274,553

Int. Cl. C07f 9/24, 9/36, 9/44 US. Cl. 260-944 3 Claims ABSTRACT 0F THE DISCLOSURE This is a division of application Ser. No. 885,263 filed Dec. 15, 1969, now US. Pat. No. 3,734,980, issued May 22, 1973.

This invention relates to the use of certain novel phosphorus containing amidine compounds as insecticides and acaricides and to a process for preparing the phosphorus containing amidines.

The compounds of the present invention that are useful as insecticides and acaricides are those having the formula:

in which R is lower alkyl having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, or lower alkoxy having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; R is lower alkoxy having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, or lower alkylthio having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; R is hydrogen, lower alkyl having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms; phenyl; mono or di-substituted phenylin which the substituents are lower alkyl having 1 to 4 carbon atoms, halogen or nitro; and X is oxygen when R is lower alkylthio andsulfur when R is lower alkoxy.

Representative compounds are as follows:

0,0-dirnethyl thionophosphoryl butyramidine 0,0-dibutyl thionophosphoryl butyramidine O,S-dimethyl phosphoryl butyramidine O,S-dibutyl phosphoryl butyramidine O-methyl, methyl thionophosphonyl butyramidine O-butyl, butyl thionophosphonyl butyramidine O-methyl, methyl phosphonyl butyramidine O-butyl, butyl phosphonyl butyramidine O-methyl, O-butyl thionophosphoryl butyramidine O-butyl, S-methyl phosphoryl butyramidine O methyl, butyl thionophosphonyl butyramidine O-butyl, methyl phosphonyl butyramidine O,S-dimethyl phosphoryl formamidine O,S-dirnethyl phosphoryl acetamidine O,S-dimethyl phosphoryl heptamidine O,S-dimethyl phosphoryl benzamidine O,S-dimethyl phosphoryl chlorbenzamidine O,S-dimethyl phosphoryl methylbenzamidine O,S-dimethyl phosphoryl nitrobenzamidine 3,825,632 Patented July 23, 1974 Compounds having the formula:

in which R and R are as defined and R is lower alkyl having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, can be prepared by the following reaction:

R -O R in which R, R and R are as stated.

Preferably about 2 moles sodium hydroxide or other suitable acid acceptor is added with heavy stirring to an aqueous solution of equal mole amounts of the reactants. The reaction is exothermic and heating is not normally necessary, but can be used. After the reaction is complete the reaction product, normally an oil, can be recovered by conventional extraction techniques.

The process of this invention for preparing compounds of the formula:

R4-S R5 in which R is lower alkyl having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, or lower alkoxy having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; R is hydrogen, lower alkyl, having 1 "to 6 carbonatoms, preferably 1 to 3 carbon atoms; phenyl, mono or di-substituted phenyl in which the substituents are lower alkyl having 1 to 4 carbon atoms, halogen or nitro; and R is lower alkyl having 1 to 4 carbon atoms by reacting a compound of the formula:

P-N=CNH, R O a in which R and R are as defined and R is lower alkyl having 1 to 4 carbon atoms with a compound of the formula:

in which R is as defined. The process of this invention can be depicted by the following equation:

R it B O No special reaction conditions are necessary for the process of this invention. It proceeds at room temperature, however, heating to reflux accelerates the reaction. Preferably, a solvent is used but is not necessary. The iodide reactant can be used as the solvent if desired, if used in large enough excess. Preferably, at least an equal mole amount of the iodide reactant should be used for a complete reaction.

Preparation of the compounds of this invention and the process of this invention is illustrated by the following examples.

EXAMPLE I Qo-dirnethyl thionophosphoryl butyramidine 24.5 gr. (0.2 mole) butyramidine-HCl is dissolved in 150 ml. water. 32.0 gr. (0.2 mole) 0,0-dimethylphosphoro chloridothioate is added and 16.0 gr. (0.4 mole) NaOH in 80 ml. H is dropped in under heavy stirring. The reaction is slightly exothermic and the temperature goes up to 39 C. Stirring is continued for one hour. The reaction product is extracted with ether four times, ether dried over MgSO filtered, and stripped. The reaction product is confirmed to be the above structure. Yield: 36.0 gr. colorless oil. N 1.5160.

EXAMPLE II O,S-dimethyl phosphoryl butyramidine TABLE]: G1

P-N=C-NH2 R1 1212 Compound number B. R X R CHsS- O H CHsS- O H CH30 S H CHaS- 0 GE CHaS- 0 Same.

CH30- S Il-CRH7- CH30- 3 CH S CHaS- O n-CaHv- C1H50- S n-C H C2H50- 8 CH;;- CH3S- 0 CH3- GH3S O Il-C3H7- Prepared in Example 1. "Prepared in Example II.

INSECTICIDAL EVALUATION TESTS The following insect species were used in evaluation tests for insecticidal activity:

(.1) Housefly (HF )Musca domestica (Linn.)

(2) Milkweed Bug (MWB) Oncopeltus fasciatus (Dallas) (3) Lygus Bug (LB)Lygus hesperus (Knight) (4) Bean Aphid (BA)-Aphis fabae (Scop.)

Jhe I-lousefly (HF) was used in evaluation tests of selected compounds as insecticides by the following procedure. A Stock solution containing ug/ml. of the toxicant in an appropriate solvent was prepared. Aliquots of this solution were combined with 1 milliliter of an acetone-peanut oil solution in a glass Petri dish and allowed to dry. The aliquots were there to achieve desired toxicant concentration ranging from 100 g. per Petri dish to that at which 50% mortality was attained. The Petri dishes were placed in a circular cardboard cage, closed on the bottom with cellophane and covered on top with cloth netting. Twenty-five female houseflies, three to five days old, were introduced into the cage and the percent mortality was recorded after 48 hours. The LD-SO values are ex pressed in terms of ,ug. per 25 female flies. The results of these insecticidal evaluation tests are given in Table II under HF.

In the Milkweed Bug (MWB) test, two-week old nymphs of Milkweed Bug (MWB) were placed in separate circular cardboard cages sealed on one end with cellophane and covered by a cloth netting on the other. Aliquots of the toxicants, dissolved in an appropriate solvent, were diluted in water containing 0.002% of a wetting agent, Sponto 22l-(a polyoxyether of alkylated phenols blended with organic sulfonates). Test concentrations ranged from 0.1% downward to that at which 50% mortality was obtained. Each of the aqueous suspensions of the candidate compound were sprayed into the insect through the cloth netting by means of a hand-spray gun. Percent mortality in each case recorded after 72 hours, and the LD-50 values expressed as percent of toxicant in the aqueous spray was recorded. These values are reported under the column MWB in Table II.

The Lygus Bug (LB) Lygus hesperus was tested similarly as the Milkweed Bug, except ten to twenty-five insects were used per cage. The caged insects were sprayed with the candidate compounds at concentrations ranging from 0.05% downward to that at which 50% mortality was obtained. After twenty-four and seventy-two hours, counts were made to determine living and dead insects. The LD-50 (percent) values were calculated. These values are reported under the column LB in Table II.

The insect species Black Bean Aphid (BA) A phis fabae (Scop.) was also employed in the test for insecticidal activity. Young nasturtium (T ropaeolum sp.) plants, approximately 2 to 3 inches tall, were used as the host plants for the bean aphid. The host plant was infested with approximately 5075 of the aphids. The test chemical was dissolved in acetone, added to water which contained a small amount of Sponto 221, an emulsifying agent. The solution was applied as a spray to the infested plants. Concentrations ranged from 0.05 percent downward until an LD-50 value was achieved. These results are given in Table II under the column BA.

ACARI'OIDAL EVALUATION TEST The two-spotted mite (28M), Tetranychus urticae (Koch) was employed in tests for miticides. Young pinto bean plants or lima bean plants (Phaseolus sp.) in the primary leaf stage were used as the host plants. The young pinto bean plants were infested with about 100 mites of various ages. Dispersions of candidate materials were prepared by dissolving 0.1 gram in 10 ml. of a suitable solvent, usually acetone. Aliquots of the toxicant solutions were suspended in water containing 0.002% v./v. Sponto 221, a polyoxyethylene ether sorbitan monolaurate, an emulsifying agent, the amount of water being sufiicient to give concentrations of active ingredient ranging from 0.05% to that at which 50% mortality was obtained. The test suspensions were then sprayed on the infested plants to the point of run off. After 7 days, mortalities of the post-embroyonic form were determined. The percentage of kill was determined by comparison with control plants which had not been sprayed with candidate compounds. The LD-50 value was calculated using wellknown procedures. These values are reported under the column 2SM-'PE in Table II.

SYSTEMIC EVALUATION TEST This test evaluates the root absorption and upward although it may be convenient to dissolve the toxicant directly in a solvent such as kerosene, fuel oil, xylene, alkylated naphthalenes or the like and use such organic solutions directly. However, the more common procedure is to employ dispersions of the toxicant in an aqueous translocatlon of the candidate systemic compound. The medmm d h composltlons may b produced by fo p e mite (25M), T etr ny W560? and ing a concentrated solution of the toxicant in a suitable the Bfiah APhid R f h PJ were organic solvent followed by dispersion in water, usually ployed in the test for systemic activlty. with the aid of surface active agents. The latter, which Young Pi bean Plants ill thfi P y lfiaf Stage w e may be anionic, cationic or nonionic types, are exempliused as host Philhts for the two-Spotted mlte- The Plhto fied by sodium stearate, potassium oleate, and other bean plants were placed in the bottles containing 200 mlalkaline metal soaps and detergents such as sodium lauryl 0f the test Solution and hfild ill P1216e With Cotton P sulfate, sodium naphthalene sulfonate, sodium alkyl naph- Only the roots were immersed. The test solu i ns W re thalenesulfonate, methyl cellulose, fatty alcohol ethers, prepared by dissolving the compounds to be tested in a polyglycol fatty acid esters and other polyoxyethylene sursuitable solvent, usually acetone, and then diluting with face active agents. The proportion of these agents comdistilled water. The final acetone concentration never exmonly comprises 1-15 by weight of the pesticidal comceeded about 1 percent. The toxicants were initially tested positions although th proportion is not critic l and may at a concentration of 10 parts per million (ppm). b varied to suit any particular sit ation. Immediately after the host plant was placed in the test It i claimed; solution, it was infested with the test species. Mortalities 1. A compound having the formula: were determined after seven days.

Young nasturtium plants were used as the host plants for the bean aphid. The host plants were transplanted into one pound of soil that had been treated with the candidate --N=CNH1 compound. Immediately after planting in the treated soil the plants were infested with the aphids. Concentrations of toxicant in the soil ranged from 10 p.p.m. per pound of soil downward until an LD value was obtained. in which 'R is lower alkyl having 1 to 4 carbon atoms or Mortality was recorded after 72 hours. 30 lower alkoxy having 1 to 4 carbon atoms; R is lower The percentage of kill of each test species was deteralkylthio having 1 to 4 carbon atoms; and R is phenyl. mined by comparison with control plants placed in dis- 2. The compound of Claim 1 in which 'R is ethyl, R is tilled Water or untreated soil. The LD-SO values were methylthio and R is phenyl. calculated. These systemic test results are reported in 3. The compound of Claim 1 wherein R is methoxy, Table II under the columns BA-sys and 2SM-sys. R is methylthio, and R is phenyl.

TABLE II (LDn values) Compound HF, LB BA, BA-Sys., PE, Sys., number g. percent percent percent p.p.1n. percent p.p.m.

1 .1 03 .03 3 .03 5 .1 01 .03 3 .03 10 3. .1 03 .03 s .03 3 4. .1 03 .05 a .03 3 .1 05 .05 .05 5. .03 .03 s .05 10 7. .1 005 .05 10 .05 a s. .1 .01 .03 3 .03 5 9. .1 .05 .03 8 .05 3 10 .05 .003 .03 3 .03 10 11 .008 .01 .003 8 .05 12 .1 .03 .05 .05 13 .1 .05 .05 10 .05 14 .1 .05 .008 3 .03 3 15- .1 .05 .03 5 .05

As those in the art are well aware, various techniques References Cited are available for incorporating the active component or UNITED STATES PATENTS toxicant in suitable pesticidal compositions. Thus, the I pesticidal compositions can be conveniently prepared in 3281321 10/1966 Malz et a1 260-944 X the form of liquids or solids, the latter preferably as homo- FOREIGN PATENTS geneous free-flowing dusts commonly formulated by admixing the active component with finely divided solids or 15l685 11/1962 260 944 carriers as exemplified by talc, natural clays, diatomaceous LORRAINE GER, p i Examiner earth, various flours such as walnut shell, wheat, soya bean, cottonseed and so forth.

Liquid compositions are also useful and normally comprise a dispersion of the toxicant in a liquid media,

R. L. RAYMOND, Assistant Examiner US. Cl. X.R. 424-211 

